US4211664A - Process for making composite magnetic material - Google Patents

Process for making composite magnetic material Download PDF

Info

Publication number
US4211664A
US4211664A US05/947,401 US94740178A US4211664A US 4211664 A US4211664 A US 4211664A US 94740178 A US94740178 A US 94740178A US 4211664 A US4211664 A US 4211664A
Authority
US
United States
Prior art keywords
process according
methacrylate
polymeric dispersant
ethylhexyl acrylate
crosslinking
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US05/947,401
Other languages
English (en)
Inventor
David R. Dixon
Jack Lydiate
Frederick J. Lubbock
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Commonwealth Scientific and Industrial Research Organization CSIRO
Orica Ltd
Original Assignee
Commonwealth Scientific and Industrial Research Organization CSIRO
ICI Australia Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Commonwealth Scientific and Industrial Research Organization CSIRO, ICI Australia Ltd filed Critical Commonwealth Scientific and Industrial Research Organization CSIRO
Application granted granted Critical
Publication of US4211664A publication Critical patent/US4211664A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin

Definitions

  • This invention relates to improved materials which are useful for the separation of small quantities of organic material from solution.
  • dissolved materials can be adsorbed from solution using solid particles which have suitable surfaces.
  • activated carbon which is used extensively throughout the chemical and process industries. It is typically used in the form of carbon black, graphite, or charcoals.
  • Other materials with suitable adsorbing properties are the various naturally-occurring clays, for example, fuller's earth, and other mineral powders. Examples of the latter include quartz, silica gel, titanium dioxide, bauxite, zeolite and many metallic oxides.
  • the adsorption process involves the physical attachment of the dissolved material to the particle surfaces and is a reversible process in that the adsorbed material can usually be removed through suitable treatment.
  • One approach is to provide a composite material which is porous and includes an adsorbent in such a way that the product to be separated from a solution will diffuse into the composite while at the same time, larger unwanted molecules will be excluded from entering the material, and wherein the said composite material is made so as to include magnetic particles whereby the composite may be easily and rapidly separated from the mixture after adsorption has taken place.
  • the composite material typically comprises adsorbent particles and magnetic particles embedded in a porous matrix of organic polymeric material, the porosity of the matrix being such as to allow small molecules of molecular weight up to several hundred to enter freely into the interstitial structure of the matrix but to exclude large molecules of higher molecular weight whereby the composite material functions selectively to adsorb dissolved materials from solution.
  • the porous matrix is made by conventional means the composite material is unsatisfactory in that it lacks dimensional stability and is in the form of very irregular particles. The procedure does not yield the product in the form of spherical particles or beads which is essential for ease of preparation, isolation, storage, and subsequent handling.
  • a process of making a composite material comprising the steps of mixing adsorbent particles and magnetic particles with a material capable of forming a crosslinked polymer and a crosslinking agent, followed by crosslinking to produce a pore size such as will exclude molecules of more than a predetermined order of molecular weight from entering the interstitial structure of the composite, said process characterized in that a polymeric dispersant is incorporated in the crosslinking step.
  • An aqueous phase containing the adsorbent and the magnetic particles is prepared by adding appropriate quantities of these materials, together with the polymeric dispersant, to an aqueous solution of the material capable of forming the crosslinked polymer, followed by thorough mixing to form an aqueous dispersion.
  • the pH of the aqueous dispersion can be adjusted to the desired level by addition of acid.
  • An organic phase is then prepared by mixing the organic dispersion medium and low molecular weight dispersant at the desired temperature.
  • the aqueous dispersion is then added to the organic phase, followed by the required amount of crosslinking agent.
  • the separation will typically comprise the steps of centrifuging with a basket centrifuge, washing in the centrifuge with an aqueous solution of a surfactant to remove the residual organic medium, transferring to another vessel for washing with a hot aqueous solution of dispersant, filtration, washing with hot water and then a solvent, followed by drying at an elevated temperature.
  • the function of the solvent is to assist in the removal of water and the choice of solvent is not narrowly critical. While we typically use acetone other solvents such as alcohols may also be used. When acetone is used a convenient drying temperature is 90° C.
  • polymeric dispersant is used in the organic phase, and a low molecular weight dispersant in the aqueous phase.
  • polymeric dispersants are used in both the aqueous and the organic phases.
  • dispersant is to some extent dependent on the phase in which it is employed.
  • suitable dispersants are polycarboxylates, for example polyacrylates and polymethacrylates. Particularly useful are copolymers of methoxypolyethyleneglycol methacrylate with either acrylic or methacrylic acid.
  • the polymeric dispersant may be a copolymer such as lauryl methacrylate/hydroxyethyl acrylate, lauryl methacrylate/hydroxyethyl methacrylate, 2-ethylhexyl acrylate/acrylic acid, 2-ethylhexyl acrylate/hydroxyethyl acrylate, 2-ethylhexyl acrylate/methacrylic acid, 2-ethylhexyl acrylate/hydroxyethyl methacrylate, 2-ethylhexyl acrylate/hydroxypropyl methacrylate or stearyl methacrylate/hydroxyethyl methacrylate, or a mixture of two or more of these.
  • any of the conventional dispersants of this type may be used.
  • Teric a polypropylene glycol ethoxylate may be used in the aqueous phase and "sorbitan trioleate may be used in the organic phase.
  • suitable matrix materials for the composite includes hydrophilic polymers derived from polyvinyl alcohol, cellulose and certain of its ethers, polyacrylamide or polymethacrylamide, polyamides such as 6,6-nylon, and polyethylene glycol.
  • Suitable crosslinking agents for these polymers can be selected by those skilled in the art.
  • reagents for crosslinking polyvinyl alcohol such as formaldehyde and other aldehydes, in particular dialdehydes such as terephthaldehyde and glutaraldehyde; dimethylol ured, tetrabutyl titanate, bis-3-methoxy propylidene, pentaerythritol, diazonium and tetrazonium salts, and boric acid. Radiation may also be used.
  • crosslinking reagents which may be used are those known to crosslink cellulose, e.g., N-methylol and N-methylol ether derivatives of amines, amides and ureas, such as dimethylol dihydroxy ethylene urea and ethyl N,N-dimethylol carbamate; diepoxides such as diglycidyl ether; ethyleneimine derivatives such as tris-(1-aziridinyl)phosphine oxide; divinyl sulphone and bis-(2-hydroxyethyl)sulphone; epichlorhydrin; phosgene and diacid dichlorides; and 4,5-dihydroxy-1,3-dimethyl-2-imidazolidinone.
  • Polyacrylamide and polymethacrylamide may also be conveniently crosslinked with epichlorhydrin.
  • the polyols may be insolubilized by reaction with di-isocyanates.
  • a catalyst is added with the crosslinking agent to promote the crosslinking.
  • Appropriate catalysts are well known to those skilled in the art, for example, in the case of a dialdehyde crosslinking agent an acid catalyst is suitable.
  • Other polymers may be used together with suitable crosslinking agents by means well known to polymer chemists.
  • the size of the particles or beads of composite adsorbent materials can be controlled by proper selection of the concentration of dispersant in the aqueous or organic phases, the stirring mode, ratio of aqueous phase to organic phase, pH, and the temperature.
  • concentration of dispersant in the aqueous or organic phases can be controlled by proper selection of the concentration of dispersant in the aqueous or organic phases, the stirring mode, ratio of aqueous phase to organic phase, pH, and the temperature.
  • the preparation of larger spherical particles is favoured by reduced stirring, a low concentration of dispersant, low temperatures, and high pH.
  • the composite may be produced by rapid crosslinking, and the final product ground as required. In this case low pH, high temperature, and vigorous stirring may usefully be employed.
  • the adsorbent particles may be desirable to protect the adsorbent particles during the process of our invention by a coating of material which can readily be removed after the adsorbent is incorporated into the composite.
  • the nature of the protecting agent will depend largely on the particular adsorbent being used. Aliphatic acids, such as acetic and propionic acids, may be used. Starches and gelatine can, for example, be removed subsequently by enzymatic means.
  • the protecting agents may be applied to the adsorbent particles by simple mixing and stirring followed by filtration and washing, or solutions of protecting agents may be sprayed onto the adsorbent particles and the solvent removed by evaporation.
  • the invention is of particular use in the food and related processing industries where trace quantities of materials need to be separated from complex mixtures of solids and liquids.
  • 2-Ethylhexyl acrylate/hydroxyethyl methacrylate copolymer 10:l mole ratio; 6 g of a 50% w/w solution in xylene) was dissolved in mineral oil (94 g). The aqueous dispersion (50 g) was adjusted to pH 1.5 with concentrated hydrochloric acid and added to the stirred organic phase. After stirring for approximately 15 minutes, glutaraldehyde (2.6 g; 25% w/w aqueous solution) was added and the mixture stirred for two hours at ambient temperature.
  • the mixture was then centrifuged and washed several times with a 1% w/w aqueous solution of a C 12 -alcohol alkoxylate.
  • the product was transferred to a reactor and stirred for one hour at 80° C. with 200 mls of 1% w/w aqueous solution of a C 12 -alcohol alkoxylate.
  • the product was then filtered, washed several times with water and finally washed with acetone before drying at 80° C.
  • Example 1 The procedure of Example 1 was repeated except that the mole-ratio of the copolymer of the organic phase was 3:1. The product was isolated in the same way.
  • Example 1 The procedure of Example 1 was repeated except that the copolymer of the organic phase was replaced by each of the following dispersants in turn.
  • Example 2 The procedure of Example 1 was repeated except that the polypropylene glycol ethoxylate in the aqueous phase was replaced by 2-ethylhexyl acrylate/hydroxyethyl methacrylate (10:1 mole ratio). The product was isolated as before.
  • Example 6 The procedure of Example 6 was repeated except that the copolymer dispersant of the organic phase was replaced by the low molecular weight surfactant, sobitan trioleate. The product was isolated as before.
  • Example 1 The procedure of Example 1 was followed except that the xylene was replaced by O-dichlorobenzene and the dispersant concentration was varied over the range of 0.1 to 1.0% w/w. The results are tabled, showing acceptable particle size distribution at all concentrations.
  • the aqueous phase was prepared as described in Example 1.
  • the organic phase was a 3% w/w solution of "Span” 85 in O-dichlorobenzene.
  • the procedure of Example 1 was then followed and after gelation the product was found to be in the form of irregular aggregates.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)
  • Colloid Chemistry (AREA)
US05/947,401 1977-10-07 1978-10-02 Process for making composite magnetic material Expired - Lifetime US4211664A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU1980/77 1977-10-07
AUPD198077 1977-10-07

Publications (1)

Publication Number Publication Date
US4211664A true US4211664A (en) 1980-07-08

Family

ID=3767197

Family Applications (1)

Application Number Title Priority Date Filing Date
US05/947,401 Expired - Lifetime US4211664A (en) 1977-10-07 1978-10-02 Process for making composite magnetic material

Country Status (6)

Country Link
US (1) US4211664A (enrdf_load_stackoverflow)
JP (1) JPS5471091A (enrdf_load_stackoverflow)
AU (1) AU547349B2 (enrdf_load_stackoverflow)
DE (1) DE2843926A1 (enrdf_load_stackoverflow)
FR (1) FR2405274B1 (enrdf_load_stackoverflow)
GB (1) GB2006789B (enrdf_load_stackoverflow)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4382982A (en) * 1979-12-07 1983-05-10 Ici Australia Limited Process for protecting magnetic particles with chromium oxide
US4447475A (en) * 1980-12-03 1984-05-08 Ici Australia Limited Process for composite polymer beads
US4661327A (en) * 1983-03-30 1987-04-28 Phillips Petroleum Company Recovery of mineral values using magnetically susceptible ion exchange agent
US4762865A (en) * 1984-03-26 1988-08-09 Gold Marvin H Epoxy coatings for computer hard disks and metal coil decoration and protection
US5298179A (en) * 1990-07-04 1994-03-29 Nippon Zeon Co., Ltd. Water absorbent, comprising magnetic material and water absorbent resin
US5349036A (en) * 1992-04-21 1994-09-20 Imperial Chemical Industries Plc Amphipathic copolymer pigment dispersants
AU719422B2 (en) * 1995-11-07 2000-05-11 Amersham Pharmacia Biotech Ab Adsorption method and separation medium
WO2001078870A1 (en) * 2000-04-16 2001-10-25 David Zornes Nano coupling magnetoadsorbent
US20120130023A1 (en) * 2009-06-23 2012-05-24 United Initiators Gmbh & Co. Kg Heat-activatable free-radical initiators and composite material which comprises magnetic particles
WO2014132107A1 (en) * 2013-02-27 2014-09-04 Empire Technology Development Llc Preparation and use of magnetic polymer nanocomposites
CN106890631A (zh) * 2017-04-20 2017-06-27 上海应用技术大学 一种pH‑磁双重响应性染料吸附剂、制备方法及其应用
US10842743B2 (en) 2016-04-08 2020-11-24 The Regents Of The University Of California Modified hyaluronic acid hydrogels and proteins for the time-controlled release of biologic agents

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1980002687A1 (en) * 1979-06-08 1980-12-11 Ici Australia Ltd Process for composite polymer beads
JPH0775703B2 (ja) * 1991-07-13 1995-08-16 ミヤマ株式会社 水中の有機溶剤除去方法
JPWO2018159724A1 (ja) * 2017-02-28 2020-12-24 東レ株式会社 有機無機混合物、その利用およびその製造方法
CN108383951A (zh) * 2018-03-06 2018-08-10 鲁东大学 一种提高聚氨酯泡沫吸油性能的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3726803A (en) * 1970-02-16 1973-04-10 Ncr Capsule wall treating process utilizing condensation polymerization and capsule product
US4082681A (en) * 1975-11-04 1978-04-04 Mita Industrial Company Magnetic developer for electrostatic photography and process for preparation thereof
US4133774A (en) * 1977-09-29 1979-01-09 Reprographic Materials, Inc. Process for preparing direct imaging pressure fixable magnetic toners

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2212174B1 (enrdf_load_stackoverflow) * 1972-12-30 1978-06-09 Toyo Jozo Kk
US4028255A (en) * 1973-01-31 1977-06-07 Ici Australia Limited Preparation of polymer composites
CH597893A5 (enrdf_load_stackoverflow) * 1973-05-31 1978-04-14 Toyo Jozo Kk
AU509548B2 (en) * 1975-12-24 1980-05-15 Commonwealth Scientific And Industrial Research Organisation Composite magnetic adsorbent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3726803A (en) * 1970-02-16 1973-04-10 Ncr Capsule wall treating process utilizing condensation polymerization and capsule product
US4082681A (en) * 1975-11-04 1978-04-04 Mita Industrial Company Magnetic developer for electrostatic photography and process for preparation thereof
US4133774A (en) * 1977-09-29 1979-01-09 Reprographic Materials, Inc. Process for preparing direct imaging pressure fixable magnetic toners

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4382982A (en) * 1979-12-07 1983-05-10 Ici Australia Limited Process for protecting magnetic particles with chromium oxide
US4447475A (en) * 1980-12-03 1984-05-08 Ici Australia Limited Process for composite polymer beads
US4661327A (en) * 1983-03-30 1987-04-28 Phillips Petroleum Company Recovery of mineral values using magnetically susceptible ion exchange agent
US4762865A (en) * 1984-03-26 1988-08-09 Gold Marvin H Epoxy coatings for computer hard disks and metal coil decoration and protection
US5298179A (en) * 1990-07-04 1994-03-29 Nippon Zeon Co., Ltd. Water absorbent, comprising magnetic material and water absorbent resin
US5349036A (en) * 1992-04-21 1994-09-20 Imperial Chemical Industries Plc Amphipathic copolymer pigment dispersants
AU719422B2 (en) * 1995-11-07 2000-05-11 Amersham Pharmacia Biotech Ab Adsorption method and separation medium
WO2001078870A1 (en) * 2000-04-16 2001-10-25 David Zornes Nano coupling magnetoadsorbent
US20120130023A1 (en) * 2009-06-23 2012-05-24 United Initiators Gmbh & Co. Kg Heat-activatable free-radical initiators and composite material which comprises magnetic particles
US8877835B2 (en) * 2009-06-23 2014-11-04 Evonik Degussa Gmbh Heat-activatable free-radical initiators and composite material which comprises magnetic particles
WO2014132107A1 (en) * 2013-02-27 2014-09-04 Empire Technology Development Llc Preparation and use of magnetic polymer nanocomposites
US9987616B2 (en) 2013-02-27 2018-06-05 Empire Technology Development Llc Preparation and use of magnetic polymer nanocomposites
US10842743B2 (en) 2016-04-08 2020-11-24 The Regents Of The University Of California Modified hyaluronic acid hydrogels and proteins for the time-controlled release of biologic agents
CN106890631A (zh) * 2017-04-20 2017-06-27 上海应用技术大学 一种pH‑磁双重响应性染料吸附剂、制备方法及其应用
CN106890631B (zh) * 2017-04-20 2019-07-19 上海应用技术大学 一种pH-磁双重响应性染料吸附剂、制备方法及其应用

Also Published As

Publication number Publication date
GB2006789B (en) 1982-09-08
JPS5471091A (en) 1979-06-07
JPS6128373B2 (enrdf_load_stackoverflow) 1986-06-30
FR2405274A1 (enrdf_load_stackoverflow) 1979-05-04
DE2843926A1 (de) 1979-04-19
FR2405274B1 (enrdf_load_stackoverflow) 1985-10-11
GB2006789A (en) 1979-05-10
AU547349B2 (en) 1985-10-17
DE2843926C2 (enrdf_load_stackoverflow) 1990-08-09
AU3995178A (en) 1980-03-27

Similar Documents

Publication Publication Date Title
US4211664A (en) Process for making composite magnetic material
US4144373A (en) Materials for the separation of organic substances from solution
US3953360A (en) Preparation of selective adsorbing particles
US3943072A (en) Separation of molecules
US5160627A (en) Process for making microporous membranes having gel-filled pores, and separations methods using such membranes
US4661411A (en) Method for depositing a fluorocarbonsulfonic acid polymer on a support from a solution
DE69027803T2 (de) Polymerträger
JP2599789B2 (ja) 水―不溶性グルコースイソメラーゼ結晶およびその製造法
EP0025639B1 (en) Process for preparing porous cellulose spherical particles
US3997482A (en) Hydrophilic polymeric carriers of biologically active compounds and method of preparing the same
US3840482A (en) Process for curing poly(vinyl alcohol)matrix beads
US3959079A (en) Insolubilization of proteins by chemical activation of a polymerized support and crosslinking of the protein to the support
US4582860A (en) Oxirane resins for enzyme immobilization
EP0485460B1 (en) Cyclodextrin polymer beads
US3623997A (en) Wall-sealing treatment for minute capsules and minute capsules having walls of sealed polymeric material
DE69208878T2 (de) Verfahren zur herstellung optisch aktiver cyanhydrine durch enzyme
US5425879A (en) Removal of base residues from poly(vinyl alcohol) reaction-slurries
JPH07330809A (ja) キトサン誘導体、それらからなる近赤外線吸収剤用組成物および近赤外線吸収剤
US4612288A (en) Oxirane resins for enzyme immobilization
JP2902032B2 (ja) 球状多孔性炭素粒子及びその製造方法
JPS62118889A (ja) 生物学的物質を固定化する方法及びこの方法によつて得られる固定化生物学的物質
JP2543081B2 (ja) シクロデキストリンの固定化方法
US4974338A (en) Drying process
RU2076871C1 (ru) Способ получения гидрофильного геля
US4279791A (en) Recovery of cerium from polymer dispersions